Cyano-complexes and salts with tetracyanonickellate(II) and N,N-bis(2-hydroxyethyl)-ethylenediamine: synthesis, IR spectra, magnetic properties, thermal analyses, and crystal structures

Abstract

Four cyano complexes, [Ni(N-bishydeten)Ni(CN)(4)](n) (c1), [Cu(N-bishydeten)(2)][Ni(CN)(4)] (c2), [Zn-2(N-bishydeten)(2)Ni(CN)(4)](n) (c3), and [Cd(N-bishydeten)(2)][Ni(CN)(4)] (c4), have been synthesized and characterized by FT-IR, elemental, and thermal analyses. The structures of c2 and c4 were determined by single-crystal X-ray diffraction studies; both structures contain isolated cations and anions. The c2 consists of [Cu(N-bishydeten)(2)](2+) with octahedrally coordinated Cu-II and diamagnetic [Ni(CN)(4)](2-), but c4 consists of [Cd(N-bishydeten)(2)](2+), in which Cd-II is eight coordinate with two tetradentate N-bishydeten and diamagnetic [Ni(CN)(4)](2-). The value of the shape measure S (degrees) indicates that the coordination geometry around Cd-II lies along D-2d [dodecahedron; (dd)], C-2v [bicapped trigonal prism; (btp)], and D-4d [square antiprism; (sap)] but close to D-2d and D-4d. Variable temperature magnetic susceptibility measurements of c1 and c2 show the presence of little antiferromagnetic interaction below 20 K. Thermal analyses reveal that first neutral N-bishydeten and then cyano ligands were liberated from the complexes.